(1,2-benzisothiazol-3-(2H)-ylidene 1,1-dioxide) acetate-terminated polymer charge-control agents for electrostatographic toners and developers

ABSTRACT

Novel (1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)acetate-terminated polymer charge-control agents are disclosed. They have the general structure (I): ##STR1## n can be as high as the number of hydroxyl groups in the polymer from which structure I is derived.

FIELD OF THE INVENTION

The present invention relates to electrostatographic developers andtoners containing charge-control agents.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is related to the following titled applications,all in the name of Wilson and Fields and all filed on the same day asthe present case:

1. U.S. Ser. No. 08/818,668, filed 14 Mar. 1997, U.S. Pat. No.5,750,715, entitled NOVEL BIS (1,2-BENZISOTHIAZOL-3(2H)-YLIDENE1,1-DIOXIDE)ACETATES! CHARGE-CONTROL AGENTS

2. U.S. Ser. No. 08/815,037, filed 14 Mar. 1997, U.S. Pat. No.5,723,248, entitled ELECTROSTATOGRAPHIC TONERS AND DEVELOPERS CONTAININGBIS (1,2-BENZISOTHIAZOL-3(2H)-YLIDENE 1,1-DIOXIDE)ACETATES!CHARGE-CONTROL AGENTS

3. U.S. Ser. No. 08/816,096, filed 14 Mar. 1997, U.S. Pat. No.5,714,295, entitled ELECTROSTATOGRAPHIC TONERS AND DEVELOPERS CONTAININGNOVEL BIS (1,2-BENZISOTHIAZOL-3(2H)-YLIDENE 1,1-DIOXIDE)ACETATES!CHARGE-CONTROL AGENTS

4. U.S. Ser. No. 08/818,811, U.S. Pat. No. 5,744,277, filed 14 Mar.1997, entitled Electrostatographic Toners And Developers Containing(1,2-Benzisothiazol-3-(2h)-Ylidene 1,1-Dioxide)Acetate-TerminatedPolymer Charge-Control Agents

BACKGROUND OF THE INVENTION

In electrography, image charge patterns are formed on a support and aredeveloped by treatment with an electrographic developer containingmarking particles which are attracted to the charge patterns. Theseparticles are called toner particles or, collectively, toner. Two majortypes of developers, dry and liquid, are employed in the development ofthe charge patterns.

In electrostatography, the image charge pattern, also referred to as anelectrostatic latent image, is formed on an insulative surface of anelectrostatographic element by any of a variety of methods. For example,the electrostatic latent image may be formed electrophotographically, byimagewise photo-induced dissipation of the strength of portions of anelectrostatic field of uniform strength previously formed on the surfaceof an electrophotographic element comprising a photoconductive layer andan electrically conductive substrate. Alternatively, the electrostaticlatent image may be formed by direct electrical formation of anelectrostatic field pattern on a surface of a dielectric material.

One well-known type of electrostatographic developer comprises a drymixture of toner particles and carrier particles. Developers of thistype are employed in cascade and magnetic brush electrostatographicdevelopment processes. The toner particles and carrier particles differtriboelectrically, such that during mixing to form the developer, thetoner particles acquire a charge of one polarity and the carrierparticles acquire a charge of the opposite polarity. The oppositecharges cause the toner particles to cling to the carrier particles.During development, the electrostatic forces of the latent image,sometimes in combination with an additional applied field, attract thetoner particles. The toner particles are pulled away from the carrierparticles and become electrostatically attached, in imagewise relation,to the latent image bearing surface. The resultant toner image can thenbe fixed, by application of heat or other known methods, depending uponthe nature of the toner image and the surface, or can be transferred toanother surface and then fixed.

Toner particles often include charge-control agents, which, desirably,provide high uniform net electrical charge to toner particles withoutreducing the adhesion of the toner to paper or other medium. Many typesof positive charge-control agents, materials which impart a positivecharge to toner particles in a developer, have been used and aredescribed in the published patent literature. In contrast, few negativecharge-control agents, materials which impart a negative charge to tonerparticles in a developer, are known.

Prior negative charge-control agents have a variety of shortcomings.Many charge-control agents are dark colored and cannot be readily usedwith pigmented toners, such as cyan, magenta, yellow, red, blue, andgreen. Some are highly toxic or produce highly toxic by-products. Someare highly sensitive to environmental conditions such as humidity. Someexhibit high throw-off or adverse triboelectric properties in some uses.Use of charge-control agents requires a balancing of shortcomings anddesired characteristics to meet a particular situation.

SUMMARY OF THE INVENTION

The invention, in its broader aspects, provides a(1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)acetate-terminated polymercharge-control agent having the general structure (I): ##STR2## n can beas high as the number of hydroxyl groups in the polymer from whichstructure I is derived. Generally n represents 0.1 to 10, preferably 1to 2.

It is an advantageous effect of the invention that negatively chargingtoners can be provided which have favorable charging characteristics.

DETAILED DESCRIPTION

The term "particle size" as used herein, or the term "size," or "sized"as employed herein in reference to the term "particles," means themedian volume weighted diameter as measured by conventional diametermeasuring devices, such as a Coulter Multisizer, sold by Coulter, Inc.of Hialeah, Fla. Median volume weighted diameter is an equivalent weightspherical particle which represents the median for a sample; that is,half of the mass of the sample is composed of smaller particles, andhalf of the mass of the sample is composed of larger particles than themedian volume weighted diameter.

The term "charge-control," as used herein, refers to a propensity of atoner addendum to modify the triboelectric charging properties of theresulting toner.

The term "glass transition temperature" or "T_(g) ", as used herein,means the temperature at which a polymer changes from a glassy state toa rubbery state. This temperature (T_(g)) can be measured bydifferential thermal analysis as disclosed in "Techniques and Methods ofPolymer Evaluation," Vol. 1, Marcel Dekker, Inc., New York, 1966.

The charge control-agents are made by a two step method comprising thesteps of

condensing 3-chloro-1,2-benzisothiazole 1,1-dioxide with2,2-dimethyl-1,3-dioxane-4,6-dione in methylene chloride in the presenceof triethylamine acid acceptor to produce5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione; and

heating 5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione with ahydroxy-terminated polymer in an inert solvent.

The chemical reaction pathway involved in this method is shown below.##STR3##

The compositions described in the invention can generally tautomerize.Thus, the general structure could, in many cases, also include thefollowing tautomeric forms: ##STR4##

For the sake of brevity, alternate tautomeric forms will not beillustrated herein. However, structural formulas should be understood tobe inclusive of alternate tautomers.

In addition to tautomeric forms, the compositions of the invention may,with respect to the 3-ylidene double bond, exist as geometric isomers.Although the configuration of the compounds of the invention areunknown, both geometric isomers are considered to fall within the scopeof the invention.

When n is greater than 1, both tautomeric forms and both geometricisomers may be present in the same polymer. ##STR5##

The following examples clarify the method of making the charge-controlagents of the invention.

EXAMPLE 1

Step 1: Preparation of 5-(1,2-Benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione.

A solution of 100.82 g (0.50 mol) of 3-chloro-1,2-benzisothiazol1,1-dioxide (prepared by the method of Stephen, et al., J. Chem. Soc.,1957, 490), 72.07 g (0.50 mol) of 2,2-dimethyl-1,3-dioxane-4,6-dione and1 L of methylene chloride was prepared and cooled in an ice/water bath.To this solution was added 101.19 g (1.00 mol) of triethylamine dropwiseover 35 min. The cooling bath was removed and the reaction mixture wasstirred for 17.5 hrs, washed with 10% HCl and twice with water. Thesolution was dried over magnesium sulfate, filtered and concentrated.The residue was washed with warm ligroine and then with acetone. Theyellow solid was recrystallized from 2-butanone, collected, washed withligroine and dried.

Step 2: Preparation of (1,2-Benzisothiazol-3-(2H)-ylidene1,1-dioxide)acetate-terminated Poly(etherified bisphenol A fumarate)(Atlac 382ES)

To a solution of 20.00 g (13.9 meq of OH) of Atlac 382ES and 100 ml oftoluene was added 4.30 g (13.9 meq) of5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione. The mixture was stirredon a steam bath for 1.5 hrs. and cooled. The resultant solution waspoured into methanol to precipitate polymer which was isolated, rinsedwith methanol and redissolved in methylene chloride and reprecipitatedin methanol. The polymer was isolated, rinsed several times withmethanol and dried. The gummy polymer was washed with water in a highspeed blender, collected and dried.

EXAMPLE 2

Preparation of (1,2-Benzisothiazol-3-(2H)-ylidene1,1-dioxide)acetate-terminated Polystyrene

To a solution of 25.00 g (5.0 mmol) of hydroxy-terminated polystyrene in100 ml of dry toluene was added 1.55 g (5.0 mmol) of5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione with 10 ml of drytoluene rinse. The mixture was heated on a steam bath for 1.5 hrs,cooled and poured into 600 ml of ligroine. The solvent was decanted fromthe precipitated polymer and the polymer was rinsed again with ligroine.The polymer was dissolved in methylene chloride, filtered throughsupercel to remove haze and poured into ligroine to precipitate polymer.The polymer was isolated, rinsed with ligroine and dried.

EXAMPLE 3

Preparation of (1,2-Benzisothiazol-3-(2H)-ylidene1,1-dioxide)acetate-terminated

Poly(tetramethylene glycol).

A mixture of 14.50 g (5.0 mmol) of poly(tetramethylene glycol)-2900 and3.10 g (10.0 mmol) of 5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione was heated on a steambath for 25 min at which time, 25 ml of THF was added and the mixturewas heated at reflux on a steam bath for 5.5 hrs. During this time,solution was achieved with a trace of flocculant insoluble material. Thereaction mixture was cooled and allowed to stand for 63.5 hrs(convenience). The reaction mixture was concentrated on a rotaryevaporator to a viscous yellow/orange residue which crystallized to agreasy solid.

Table 1 lists the polymeric charge-control agents prepared in examples1-3.

Other polymers that can be used to make the(1,2-benzisothiazol-3-(2H)-ylidene 1,1-dioxide)acetate-terminatedpolymer charge-control agents are:

(a) Hydroxy-terminated polyesters derived from reaction of dicarboxylicacids, and esters thereof, with glycols and bisphenols, lactones withalcohols or glycols and the like where a portion or essentially allterminal groups are hydroxyl groups.

(b) Hydroxy-terminated polyethers derived from ring openingpolymerization of cyclic ethers. Such polymers being represented bypoly(ethylene glycol), poly(propylene glycol), poly(tetramethyleneglycol) and the like.

(c) Hydroxy-terminated polyvinyls formed, for example, by the anionicpolymerization of vinyl monomers such as styrene.

Other hydroxy terminated polymers which are considered useful precursorsto the polymeric charge-control agents of the invention include branchedpolyesters with hydroxyl end groups, polyvinylalcohol,poly(2-hydroxyethyl methacrylate), phenol-formaldehyde resins,hydroxy-terminated polyethylene/butylene.

The toner of the invention includes a charge-control agent of theinvention, in an amount effective to modify, and improve the propertiesof the toner. It is preferred that a charge-control agent improve thecharging characteristics of a toner, so the toner quickly charges to anegative value having a relatively large absolute magnitude and thenmaintains about the same level of charge. The compositions used in thetoners are negative charge-control agents, thus the toners of theinvention achieve and maintain negative charges.

It is also preferred that a charge-control agent improve the chargeuniformity of a toner composition, that is, it insures thatsubstantially all of the individual toner particles exhibit atriboelectric charge of the same sign with respect to a given carrier.It is also preferred that a charge-control agent be colorless,particularly for use in light colored toners. The charge-control agentsof the invention are generally colorless. It is also preferred that acharge-control agent be metal free. The charge-control agents of theinvention are metal free. Preferred materials described herein are basedupon an evaluation in terms of a combination of characteristics ratherthan any single characteristic.

The binders used in formulating the toners of the invention with thecharge-controlling additive of the present invention are polyestershaving a glass transition temperature of 50° to 100° C. and a weightaverage molecular weight of 10,000 to 100,000. The polyesters areprepared from the reaction product of a wide variety of diols anddicarboxylic acids. Some specific examples of suitable diols are:1,4-cyclohexanediol; 1,4-cyclohexanedimethanol;1,4-cyclohexanediethanol; 1,4-bis(2-hydroxyethoxy)cyclohexane;1,4-benzenedimethanol; 1,4-benzenediethanol; norbornylene glycol;decahydro-2,6-naphthalenedimethanol; bisphenol A; ethylene glycol;diethylene glycol; triethylene glycol; 1,2-propanediol, 1,3-propanediol;1,4-butanediol; 2,3-butanediol; 1,5-pentanediol; neopentyl glycol;1,6-hexanediol; 1,7-heptanediol; 1,8-octanediol; 1,9-nonanediol;1,10-decanediol; 1,12-dodecanediol; 2,2,4-trimethyl-1,6-hexanediol;4-oxa-2,6-heptanediol and etherified diphenols.

Suitable dicarboxylic acids include: succinic acid; sebacic acid;2-methyladipic acid; diglycolic acid; thiodiglycolic acid; fumaric acid;adipic acid; glutaric acid; cyclohexane-1,3-dicarboxylic acid;cyclohexane-1,4-dicarboxylic acid; cyclopentane-1,3-dicarboxylic acid;2,5-norbornanedicarboxylic acid; phthalic acid; isophthalic acid;terephthalic acid; 5-butylisophthalic acid; 2,6-naphthalenedicarboxylicacid; 1,4-naphthalenedicarboxylic acid; 1,5-naphthalenedicarobxylicacid; 4,4'-sulfonyldibenzoic acid; 4,4'-oxydibenzoic acid;binaphthyldicarboxylic acid; and lower alkyl esters of the acidsmentioned.

Polyfunctional compounds having three or more carboxyl groups, and threeor more hydroxyl groups are desirably employed to create branching inthe polyester chain. Triols, tetraols, tricarboxylic acids, andfunctional equivalents, such as pentaerythritol,1,3,5-trihydroxypentane,1,5-dihydroxy-3-ethyl-3-(2-hydroxyethyl)pentane, trimethylolpropane,trimellitic anhydride, pyromellitic dianhydride, and the like aresuitable branching agents. Presently preferred polyols are glycerol andtrimethylolpropane. Preferably, up to about 15 mole percent, preferably5 mole percent, of the reactant diol/polyol or diacid/polyacid monomersfor producing the polyesters can be comprised of at least one polyolhaving a functionality greater than two or poly-acid having afunctionality greater than two.

Variations in the relative amounts of each of the respective monomerreactants are possible for optimizing the physical properties of thepolymer.

The polyesters of this invention are conveniently prepared by any of theknown polycondensation techniques, e.g., solution polycondensation orcatalyzed melt-phase polycondensation, for example, by thetransesterification of dimethyl terephthalate, dimethyl glutarate,1,2-propanediol and glycerol.

The polyesters also can be prepared by two-stage polyesterificationprocedures, such as those described in U.S. Pat. No. 4,140,644 and U.S.Pat. No. 4,217,400. The latter patent is particularly relevant, becauseit is directed to the control of branching in polyesterification. Insuch processes, the reactant glycols and dicarboxylic acids, are heatedwith a polyfunctional compound, such as a triol or tricarboxylic acid,and an esterification catalyst in an inert atmosphere at temperatures of190° to 280° C., especially 200° to 240° C. Subsequently, a vacuum isapplied, while the reaction mixture temperature is maintained at 220° to240° C., to increase the product's molecular weight.

The degree of polyesterification can be monitored by measuring theinherent viscosity (I.V.) of samples periodically taken from thereaction mixture. The reaction conditions used to prepare the polyestersshould be selected to achieve an I.V. of 0.10 to 0.80 measured inmethylene chloride solution at a concentration of 0.25 grams of polymerper 100 milliliters of solution at 25° C. An I.V. of 0.10 to 0.60 isparticularly desirable to insure that the polyester has a weight averagemolecular weight of 10,000 to 100,000, preferably 55,000 to 65,000, abranched structure and a Tg in the range of about 50° to about 100° C.Amorphous polyesters are particularly well suited for use in the presentinvention. After reaching the desired inherent viscosity, the polyesteris isolated and cooled.

One useful class of polyesters comprises residues derived from thepolyesterification of a polymerizable monomer composition comprising:

a dicarboxylic acid-derived component comprising:

about 75 to 100 mole % of dimethyl terephthalate and

about 0 to 25 mole % of dimethyl glutarate and a diol/poly-derivedcomponent comprising

about 90 to 100 mole % of 1,2-propanediol and

about 0 to 10 mole % of glycerol.

Many of the aforedescribed polyesters are disclosed in the patent toAlexandrovich et al, U.S. Pat. No. 5,156,937.

Another useful class of polyesters is the non-linear reaction product ofa dicarboxylic acid and a polyol blend of etherified diphenols disclosedin U.S. Pat. Nos. 3,681,106; 3,709,684; and 3,787,526.

The etherified diphenols of U.S. Pat. No. 3,787,526 have the formula:##STR6## wherein z is 0 or 1; R is an alkylene radical containing from 1to 5 carbon atoms, a sulfur atom, an oxygen atom, or a radicalcharacterized by the formula: ##STR7## R₁ is an ethylene or propyleneradical; x and y are integers with the proviso that the sum of x and yin said polyol blend is an average of from about 2.0 to about 7; andeach A is individually selected from the group consisting of hydrogenand halogen atoms; and from about 0.01 to about 2.0 mol percent of analkoxylated polyhydroxy compound, which polyhydroxy compound containsfrom 3 to 12 carbon atoms and from 3 to 9 hydroxyl groups and whereinthe alkoxylated polyhydroxy compound contains from 1 to 10 mols ofoxyalkylene groups per hydroxyl group of said polyhydroxy compound andsaid oxyalkylene radical is ethylene or propylene;

the number of carboxyl groups of said dicarboxylic acid to the number ofhydroxyl groups of said polyol blend is in a ratio of from about 1.2 toabout 0.8.

Among those diphenols which are contemplated as the base for theetherified diphenols used in the preparation of the polyesters are:

2,2-bis(1-hydroxyphenyl) propane;

bis(4-hydroxyphenyl) ethane;

3,3-bis(4-hydroxyphenyl) pentane;

p,p'-dihydroxydiphenol;

4,4'-dihydroxydiphenyl ether;

4,4'-dihydroxydiphenyl thioether;

4,4'-dihydroxydiphenyl ketone;

2,2'-bis(4-hydroxy-2,6-dichlorophenyl) propane; 2-fluoro-4-hydroxyphenylsulfoxide;

4,4'-dihydroxydiphenyl sulfone;

2,3,6-dichlorobromo-4-hydroxyphenyl-2,6-dichloro-4-hydroxyphenylmethane; and

2,2-bis(2,3,5,6-tetrabromo-4-hydroxyphenyl)butane.

A preferred group of etherified bisphenols within the classcharacterized by the above formula in U.S. Pat. No. 3,787,526 arepolyoxypropylene 2,2'-bis(4-hydroxyphenyl) propane and polyoxyethyleneor polyoxypropylene, 2,2-bis(4-hydroxy, 2,6-dichlorophenyl) propanewherein the number of oxyalkylene units per mol of bisphenol is from 2.1to 2.5.

The etherified diphenols disclosed in U.S. Pat. No. 3,709,684 arerepresented by the formula: ##STR8##

In this formula w represents an integer of 0 or 1; R is an alkyleneradical of one to five carbon atoms, oxygen, sulfur or a divalentradical represented by the formula: ##STR9##

Each A is individually selected from either a halogen atom or a hydrogenatom; the letters m and n are integers from 0 through 6 with the provisothat the sum of m and n is at least about 2 and less than 7; and X and Yare radicals which are individually selected from the following group:alkyl radicals of one to three carbon atoms, a phenyl radical, or ahydrogen atom; provided that in any X and Y pair on adjacent carbonatoms either X or Y is a hydrogen atom. A preferred group of etherifieddiphenols within the above formula include those where each A is eithera chlorine atom or hydrogen and/or R is an alkylene radical containingone to three carbon atoms, and X and Y are either hydrogen or a methylradical. In this preferred group the average sum of n and m is at mostabout 3. Examples of etherified diphenols within the above formulainclude the following:

polyoxyethylene(3)-2,2-bis(4-hydroxyphenyl) propane;polyoxystyrene(6)-bis(2,6-dibromo-4-hydroxyphenyl) methane;polyoxybutylene(2.5)-bis(4-hydroxyphenyl) ketone;polyoxyethylene(3)-bis(4-hydroxphenyl) ether;polyoxystyrene(2.8)-bis(2,6-dibromo-4-hydroxyphenyl) thioether;polyoxypropylene(3)bis(4-hydroxyphenyl) sulfone;polyoxystyrene(2)-bis(2,6-dichloro-4-hydroxyphenyl) ethane;polyoxyethylene(3)-bis(4-hydroxyphenyl) thioether;polyoxy-propylene(4)-4,4'-bisphenol;polyoxyethylene(7)-bis(2,3,6-trifluorodichloro-4-hydroxyphenyl) ether;polyoxyethylene(3.5)-4,4-bis(4-hydroxyphenyl) pentane;polyoxystyrene(4)-2-fluoro-4-hydroxyphenyl, 4-hydroxyphenyl sulfoxide;and polyoxybutylene(2)-3,2-bis(2,3,6-tribromo-4-hydroxyphenyl) butane.

A class of readily available etherified diphenols within the aboveformula from U.S. Pat. No. 3,709,684 are the bisphenols. A preferredclass of etherified bisphenols are those prepared from2,2-bis(4-hydroxy-phenyl) propane or the corresponding2,6,2',6'-tetrachloro or tetrafluoro bisphenol alkoxylated with from 2to 4 mols of propylene or ethylene oxide per mol of bisphenol.

The etherified diphenols disclosed in U.S. Pat. No. 3,681,106 have theformula: ##STR10## wherein z is 0 or 1, R is an alkylene radicalcontaining from 1 to 5 carbon atoms, a sulfur atom, an oxygen atom,##STR11## X and Y are individually selected from the group consisting ofalkyl radicals containing from 1 to 3 carbon atoms, hydrogen, and aphenyl radical with the limitation that at least X or Y is hydrogen inany X and Y pair on adjacent carbon atoms, n and m are integers with theproviso that the average sum of n and m is from about 2 to about 7; andeach A is either a halogen atom or a hydrogen atom. An average sum of nand m means that in any polyol blend some of the etherified diphenolswithin the above formula may have more than 7 repeating ether units butthat the average value for the sum of n and m in any polyhydroxycomposition is from 2 to 7. Examples of compounds within the abovegeneral formula from U.S. Pat. No. 3,681,106 are:

polyoxystyrene(6)-2,2-bis(4-hydroxyphenyl) propane;

polyhydroxybutylene(2)-2,2-bis(4-hydroxyphenyl) propane;

polyoxyethylene(3)-2,2-bis(4-hydroxyphenyl) propane;

polyoxypropylene(3)-bis(4-hydroxyphenyl) thioether;

polyoxyethylene(2)-2,6-dichloro-4-hydroxyphenyl,2',3',6'-trichloro-4'-hydroxyphenyl methane;

polyoxypropylene(3)-2-bromo-4-hydroxyphenyl, 4'-hydroxyphenyl ether;

polyoxyethylene(2.5)-p,p-bisphenol;

polyoxybutylene(4)-bis(4-hydroxyphenyl) ketone;

polyoxystyrene(7)-bis(4-hydroxyphenyl) ether;

polyoxypentylene(3)-bis(2,6-diiodo-4-hydroxyphenyl) propane; and

polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl) propane.

A preferred group of said etherified diphenols are those where theaverage sum of n and m is from about 2 to about 3. Thus, although thesum of n and m in a given molecule may be as high as about 20, theaverage sum in the polyol composition will be about 2 to about 3.Examples of these preferred etherified diphenols include:

polyoxyethylene(2.7)-4-hydroxyphenyl-2-chloro-4-hydroxyphenyl ethane;

polyoxyethylene(2.5)-bis(2,6-dibromo-4-hydroxyphenyl) sulfone;

polyoxypropylene(3)-2,2-bis(2,6-difluoro-4-hydroxyphenyl) propane; and

polyoxyethylene(1.5)-polyoxypropylene(1.0)-bis(4-hydroxyphenyl) sulfone.

A preferred polyhydroxy composition used in said polyester resins arethose polyhydroxy compositions containing up to 2 mol percent of anetherified polyhydroxy compound, which polyhydroxy compound containsfrom 3 to 12 carbon atoms and from 3 to 8 hydroxyl groups. Exemplary ofthese polyhydroxy compounds are sugar alcohols, sugar alcoholanhydrides, and mono and disaccharides. A preferred group of saidpolyhydroxy compounds are soribitol, 1,2,3,6-hexantetrol; 1,4-sorbitan;pentaerythritol, xylitol, sucrose, 1,2,4-butanetriol,1,2,5-pentanetriol; xylitol; sucrose, 1,2,4-butanetriol; and erythro andthreo 1,2,3-butanetriol. Said etherified polyhydroxy compounds arepropylene oxide or ethylene oxide derivatives of said polyhydroxycompounds containing up to about 10 molecules of oxide per hydroxylgroup of said polyhydroxy compound and preferably at least one moleculeof oxide per hydroxyl group. More preferably the molecules of oxide perhydroxyl group is from 1 to 1.5. Oxide mixtures can readily be used.Examples of these derivatives include polyoxyethylene(20)pentaerythritol, polyoxypropylene(6) sorbitol, polyoxyethylene(65)sucrose, and polyoxypropylene(25) 1,4-sorbitan. The polyester resinsprepared from this preferred polyhydroxy composition are more abrasionresistant and usually have a lower liquid point than other crosslinkedpolyesters herein disclosed.

Polyesters that are the non-linear reaction product of a dicarboxylicacid and a polyol blend of etherified polyhydroxy compounds, discussedabove, are commercially available from Reichold Chemical Company. Toillustrate the invention the examples provided herein use anpoly(etherified bisphenol A fumarate) sold as Atlac 382ES by Reichold.

An optional but preferred component of the toners of the invention iscolorant: a pigment or dye. Suitable dyes and pigments are disclosed,for example, in U.S. Pat. No. Re. 31,072 and in U.S. Pat. Nos.4,160,644; 4,416,965; 4,414,152; and 2,229,513. One particularly usefulcolorant for toners to be used in black and white electrostatographiccopying machines and printers is carbon black. Colorants are generallyemployed in the range of from about 1 to about 30 weight percent on atotal toner powder weight basis, and preferably in the range of about 2to about 15 weight percent.

The toners of the invention can also contain other additives of the typeused in previous toners, including leveling agents, surfactants,stabilizers, and the like. The total quantity of such additives canvary. A present preference is to employ not more than about 10 weightpercent of such additives on a total toner powder composition weightbasis.

The toners can optionally incorporate a small quantity of low surfaceenergy material, as described in U.S. Pat. Nos. 4,517,272 and 4,758,491.Optionally the toner can contain a particulate additive on its surfacesuch as the particulate additive disclosed in U.S. Pat. No. 5,192,637.

A performed mechanical blend of particulate polymer particles,charge-control agent, colorants and additives can, alternatively, beroll milled or extruded at a temperature sufficient to melt blend thepolymer or mixture of polymers to achieve a uniformly blendedcomposition. The resulting material, after cooling, can be ground andclassified, if desired, to achieve a desired toner powder size and sizedistribution. For a polymer having a "T_(g) " in the range of about 50°C. to about 120° C., a melt blending temperature in the range of about90° C. to about 150° C. is suitable using a roll mill or extruder. Meltblending times, that is, the exposure period for melt blending atelevated temperature, are in the range of about 1 to about 60 minutes.After melt blending and cooling, the composition can be stored beforebeing ground. Grinding can be carried out by any convenient procedure.For example, the solid composition can be crushed and then ground using,for example, a fluid energy or jet mill, such as described in U.S. Pat.No. 4,089,472. Classification can be accomplished using one or twosteps.

In place of blending, the polymer can be dissolved in a solvent in whichthe charge-control agent and other additives are also dissolved or aredispersed. The resulting solution can be spray dried to produceparticulate toner powders. Limited coalescence polymer suspensionprocedures as disclosed in U.S. Pat. No. 4,833,060 are particularlyuseful for producing small sized, uniform toner particles.

The toner particles have an average diameter between about 0.1micrometers and about 100 micrometers, and desirably have an averagediameter in the range of from about 1.0 micrometer to 30 micrometers forcurrently used electrostatographic processes. The size of the tonerparticles is believed to be relatively unimportant from the standpointof the present invention; rather the exact size and size distribution isinfluenced by the end use application intended. So far as is now known,the toner particles can be used in all known electrostatographic copyingprocesses.

The amount of charge-control agent used typically is in the range ofabout 0.2 to 20.0 parts per hundred parts of the binder polymer. Inparticularly useful embodiments, the charge-control agent is present inthe range of about 1.0 to 14.4 parts per hundred. In some embodimentsthe polymeric charge-control agent constitutes the entire binder.

The developers of the invention include carriers and toners of theinvention. Carriers can be conductive, non-conductive, magnetic, ornon-magnetic. Carriers are particulate and can be glass beads; crystalsof inorganic salts such as ammonium chloride, or sodium nitrate;granules of zirconia, silicon, or silica; particles of hard resin suchas poly(methyl methacrylate); and particles of elemental metal or alloyor oxide such as iron, steel, nickel, carborundum, cobalt, oxidized ironand mixtures of such materials. Examples of carriers are disclosed inU.S. Pat. Nos. 3,850,663 and 3,970,571. Especially useful in magneticbrush development procedures are iron particles such as porous iron,particles having oxidized surfaces, steel particles, and other "hard"and "soft" ferromagnetic materials such as gamma ferric oxides orferrites of barium, strontium, lead, magnesium, copper, zinc oraluminum. Copper-zinc ferrite powder is used as a carrier in theexamples hereafter. Such carriers are disclosed in U.S. Pat. Nos.4,042,518; 4,478,925; and 4,546,060.

Carrier particles can be uncoated or can be coated with a thin layer ofa film-forming resin to establish the correct triboelectric relationshipand charge level with the toner employed. Examples of suitable resinsare the polymers described in U.S. Pat. Nos. 3,547,822; 3,632,512;3,795,618 and 3,898,170 and Belgian Patent No. 797,132. Polymeric silanecoatings can aid the developer to meet the electrostatic forcerequirements mentioned above by shifting the carrier particles to aposition in the triboelectric series different from that of the uncoatedcarrier core material to adjust the degree of triboelectric charging ofboth the carrier and toner particles. The polymeric silane coatings canalso reduce the frictional characteristics of the carrier particles inorder to improve developer flow properties; reduce the surface hardnessof the carrier particles to reduce carrier particle breakage andabrasion on the photoconductor and other components; reduce the tendencyof toner particles or other materials to undesirably permanently adhereto carrier particles; and alter electrical resistance of the carrierparticles.

In a particular embodiment, the developer of the invention contains fromabout 1 to about 20 percent by weight of toner of the invention and fromabout 80 to about 99 percent by weight of carrier particles. Usually,carrier particles are larger than toner particles. Conventional carrierparticles have a particle size of from about 5 to about 1200 micrometersand are generally from 20 to 200 micrometers.

The toners of the invention are not limited to developers which havecarrier and toner, and can be used, without carrier, as single componentdeveloper.

The toner and developer of the invention can be used in a variety ofways to develop electrostatic charge patterns or latent images. Suchdevelopable charge patterns can be prepared by a number of methods andare then carried by a suitable element. The charge pattern can becarried, for example, on a light sensitive photoconductive element or anon-light-sensitive dielectric surface element, such as an insulatorcoated conductive sheet. One suitable development technique involvescascading developer across the electrostatic charge pattern. Anothertechnique involves applying toner particles from a magnetic brush. Thistechnique involves the use of magnetically attractable carrier cores.After imagewise deposition of the toner particles the image can befixed, for example, by heating the toner to cause it to fuse to thesubstrate carrying the toner. If desired, the unfused image can betransferred to a receiver such as a blank sheet of copy paper and thenfused to form a permanent image.

The invention is further illustrated by the following Examples.

Preparation of Toners

A poly(etherified bisphenol A fumarate) was heated and melted on a 4inch two roll melt compounding mill. The polyester base polymer wasAtlac 382ES manufactured by Reichold Chemical. One roll was heated andcontrolled to a temperature of 120° C., the other roll was cooled withchilled water. After melting the polyester, the charge-control agent andany pigments were added to the melt. A typical batch formula was 50 g ofpolyester and 0.5 g of charge-control agent, giving a product with 1part charge-control agent per 100 parts of polymer. The melt wascompounded for 20 minutes, peeled from the mill and cooled. The melt wasthen coarse ground to approximately 2 mM in a laboratory mechanical milland then fine ground in a Trost TX air jet mill. The ground toner had amean particle size of approximately 8.5 μm.

Clear toners (toners containing only charge-control agent and polyester)were made for each charge-control agent example. A control tonercontaining no charge-control agent was made by the same compounding andgrinding procedure.

Black and magenta toners, with and without(control) charge-controlagents, were made using the same technique.

Black toners were made using Cabot Regal 300 carbon black added to thepolymer melt while roll milling. Carbon black concentrations were 5parts carbon per 100 parts of polyester.

Magenta toners were made by adding a magenta pigment to the melt whilemelt compounding. Pigment Red 57:1 was used. PR 57:1 is thepigment/polyester concentrate, Luperton RED 1255 made by BASFCorporation. Pigments were used in the concentration of 8.4 partspigment/100 parts polymer.

Preparation of Developers

Developers (toners and carrier particles) were made for each preparedtoner composition, including control toners. The carrier was acopper-zinc ferrite powder with a particle size of approximately 60 μm.The ferrite particles were coated with a polysilane. The carrier wasmade by Powdertech Corporation. Developers were made by blending 20 g ofcarrier and 0.8 g of toner. The toner concentration was 4 parts tonerper 100 parts carrier.

Surface Treatment

Developers containing black or magenta pigmented toners are frequentlysurface treated with silica to improve their powder flow properties.Accordingly developers, containing black or magenta toners and carriers,were surface treated by adding amorphous silica powder to the carrierand toner blend. The silica had a specific BET surface area of 110 m²/g. Degussa R972 silica was used for surface treatment. For each surfacetreated developer, 0.004 g of silica was added to a mixture of 0.8 g oftoner and 20 g of carrier to give a silica concentration of 0.5 partsper 100 parts of toner.

Measurement of Toner Charge

The various developers were separately exercised by shaking a vialcontaining 20 g of developer on a wrist shaker with an amplitude ofapproximately 11 cm and frequency of 120 Hz. The developer was shakenand samples taken after 2, 10, 60, and 120 minutes of exercising.

A weighed sample (about 0.15 g) of the exercised developer was placed ona 50 micron mesh wire screen. Toner was removed by passing a vacuum tubecontaining a fine mesh filter across the backside of the screen. Thetube was brass and insulated from the screen by a plastic tip. The brasstube body was connected to an electrometer that measured the totalcharge in microcoulombs on the toner collected by the filter. After allthe toner was removed from the carrier the total charge was recorded andthe filter containing toner removed and weighed. The charge to massratio (Q/m) of the toner was calculated by dividing the total charge bythe toner weight to give Q/m in microcoulombs per gram (μc/g).

Results of these measurements for clear, black and magenta toners arepresented hereafter in Table 1.

Evaluation of Charging Properties

Effective charge-control agents are ones that increase the absolutecharge level of the toner relative to the control toner containing nocharge-control agent. The level of charge can generally be increased byincreasing the concentration of the charge-control agent.

Surface treatment of toner with fine silica improves the image qualityof prints made with it, and also effects the triboelectric properties ofthe toner. Silica surface treatment has the effect of raising theabsolute initial charge/mass level of a toner. The charge level of ablack surface treated toner containing no charge-control agent measuredat 2 and 10 minutes is significantly higher than the same formulationwith no surface treatment. Surface treatment has little to no effect onthe Q/m of toners after 60 and 120 minutes exercise time.

Effective charge-control agent in silica surface treated toners raisesthe Q/m of toners that have been exercised 60 and 120 minutes. Suchtoners will give more consistent print densities and image quality inelectrophotographic printers.

Toners that charge rapidly and maintain that charge with extendedexercise time are desirable. The initial Q/m indicates if the toner ischarging rapidly. Measurements at 60 and 120 minutes indicate whetherthe material is maintaining a constant charge with life. This exercisetime represents the mixing that the developer experiences in aelectrophotographic printer.

Exercised toners that show a little or no decrease in Q/m over time arepreferred over formulations that show a large decrease. A toner with aconstant charge level will maintain a consistent print density whencompared to a formulation that does not have a constant charge/masslevel.

Table 1 establishes that the (1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)acetate-terminated polymers are effective charge-controlagents for clear, black and color toners.

                  TABLE 1                                                         ______________________________________                                        (1,2-Benzisothiazol-3-(2H)-ylidene 1,1-dioxide)acetate-terminated             Polymeric Charge-Control Agents                                               Charge-control                                                                              -Q/m                                                            agent     pph     2 min   10 min 60 min 120 min                               ______________________________________                                        CLEAR TONER                                                                   Control   0.0     36.2    38.9   39.7   40.0                                  Example 1 3.6     30.2    32.8   39.2   39.1                                            14.4    34.3    37.1   39.5   41.0                                  Example 2 0.25    38.9    40.5   46.2   44.1                                            1.0     40.3    40.1   46.9   46.0                                  Example 3 0.25    25.8    33.0   42.1   43.6                                            1.0     27.6    31.8   41.5   42.4                                  BLACK TONER WITH SILICA                                                       Control   0.0     29.8    28.8   22.8   16.3                                  Example 1 1.0     30.0    28.4   22.7   19.7                                            4.0     29.8    29.7   22.0   18.6                                  MAGENTA (PR 57:1) TONER WITH SILICA                                           Control   0.0     45.1    40.2   34.8   34.2                                  Example 1 3.6     50.3    46.8   41.3   43.8                                            14.4    45.7    45.1   45.6   46.5                                  ______________________________________                                    

While specific embodiments of the invention have been shown anddescribed herein for purposes of illustration, the protection affordedby any patent which may issue upon this application is not strictlylimited to a disclosed embodiment; but rather extends to modificationsand arrangements which fall fairly within the scope of the claims whichare appended hereto.

It is claimed:
 1. A (1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)acetate-terminated polymer charge-control agent having thegeneral structure (I): ##STR12## wherein n can be as high as the numberof hydroxyl groups in the polymer from which structure I is derived. 2.The (1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)acetate-terminatedpolymer charge-control agent of claim 1 wherein n represents 0.1 to 10.3. A method of making (1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)acetate-terminated polymers by a two step procedurecomprising the steps ofcondensing 3-chloro-1,2-benzisothiazole1,1-dioxide with 2,2-dimethyl-1,3-dioxane-4,6-dione in methylenechloride in the presence of triethylamine acid acceptor to produce5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione; and heating5-(1,2-benzisothiazol-3(2H)-ylidene1,1-dioxide)-2,2-dimethyl-1,3-dioxane-4,6-dione with ahydroxy-terminated polymer in an inert solvent.
 4. The(1,2-benzisothiazol-3(2H)-ylidene 1,1-dioxide)acetate-terminated polymercharge-control agent of claim 1 or 2 wherein the polymer in structure Iis selected from the group consisting of:(a) hydroxy-terminatedpolyvinyls; (b) branched polyesters with hydroxyl end groups; (c)polyvinylalcohol; (d) poly(2-hydroxyethyl methacrylate); (e)phenol-formaldehyde resins and (f) hydroxy-terminatedpolyethylene/butylene.
 5. 2-benzisothiazol-3(2H)-ylidene1,1-dioxide)acetate-terminated polymer charge-control agent of claim 1wherein the polymer is selected from the group consisting ofpoly(etherified bisphenol A fumarate), hydroxy terminated polystyreneand polytetramethylene glycol.